Evolution of a Strategy for the Total Synthesis of (+)-Cornexistin.

Autor: Wildermuth RE; Institute of Organic Chemistry and Center for Molecular Biosciences, Leopold-Franzens-University Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria.; Department of Chemistry and Pharmacy, Ludwig-Maximilians-University Munich, Butenandtstrasse 5-13, 81377, Munich, Germany., Steinborn C; Institute of Organic Chemistry and Center for Molecular Biosciences, Leopold-Franzens-University Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria., Barber DM; Research & Development, Weed Control Chemistry, Bayer AG Crop Science Division Industriepark Höchst, 65926, Frankfurt am Main, Germany., Mühlfenzl KS; Department of Chemistry and Pharmacy, Ludwig-Maximilians-University Munich, Butenandtstrasse 5-13, 81377, Munich, Germany., Kendlbacher M; Institute of Organic Chemistry and Center for Molecular Biosciences, Leopold-Franzens-University Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria., Mayer P; Department of Chemistry and Pharmacy, Ludwig-Maximilians-University Munich, Butenandtstrasse 5-13, 81377, Munich, Germany., Wurst K; Institute of General, Inorganic & Theoretical Chemistry, Leopold-Franzens-University Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria., Magauer T; Institute of Organic Chemistry and Center for Molecular Biosciences, Leopold-Franzens-University Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2021 Aug 19; Vol. 27 (47), pp. 12181-12189. Date of Electronic Publication: 2021 Jul 07.
DOI: 10.1002/chem.202101849
Abstrakt: Herein is given a full account of the evolution of the first total synthesis of (+)-cornexistin. Initial efforts were based on masking the reactive maleic anhydride moiety as a 3,4-substituted furan and on forming the nine-membered carbocycle in an intramolecular Conia-ene or Nozaki-Hiyama-Kishi (NHK) reaction. Those strategies suffered from low yields and were jeopardized by a late-stage installation of the Z-alkene, as well as the stereocenters along the eastern periphery. These issues were addressed by employing a chiral-pool strategy that involved construction of the crucial stereocenters at C2, C3 and C8 at an early stage with installation of the maleic anhydride as late as possible. The successful approach featured an intermolecular NHK coupling to install the Z-alkene, a syn-Evans-aldol reaction to forge the stereocenters along the eastern periphery, an intramolecular allylic alkylation to close the nine-membered carbocycle, and a challenging stepwise hydrolysis of a β-keto nitrile to furnish the maleic anhydride.
(© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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